DE19608354A1 - Biodegradable polymer inclusion compounds of renewable raw material with good, variable mechanical properties - Google Patents

Abstract

The polymer inclusion compounds (I) have host molecules (II) of natural or chemically modified amylose and guest molecules (III) that consist of polymers of monomers which convert the host molecules into a canal structure and polymerise in this canal structure. Also claimed are copolymers containing (I).

Description

The invention relates to polymeric inclusion compounds from host and Guest molecules and processes for their production. There has been for a long time Efforts to develop new polymeric materials based on both renewable raw materials, as well as easily after use are biodegradable. The advantages of such materials are that Growing the necessary vegetable raw materials an alternative for the Agriculture represents and the production and disposal of such materials Is CO₂ neutral and therefore environmentally friendly. With good material properties such materials offer good market opportunities. Quality Material properties in this context means that the material is simple, preferably thermoplastic, processable, on the other hand has sufficient strength and dimensional stability. To achieve this goal achieve, for example, two or more different polymers combined with each other. One or all of the polymers used can be used based on renewable raw materials. So is in PCT / EP92 / 00959 Composite material described which consists of starch and polyester Coextrusion is produced. There are polyester with 2 to 22 Carbon atoms per monomer unit, their copolymers with one another and their copolymers with polyurethanes, polyamide polyurethanes, polyamides, Polyester amides, cellulose, amylose, starch, polyethers, polyvinylpyrrolidones and polyacrylates. The material is manufactured by Coextrusion of the two polymers and any auxiliaries in commercially available Extruding. It can be used to manufacture materials that are used as Fibers, foils, films and workpieces can be found. The limits of Applicability is determined by the material properties of the composite.  

As with all polymer blends, so does the coextrusion of starch or their derivatives with the polymers mentioned the problem of Segregation on. This means that the individual components are in Separate microscopic or macroscopic domain structures. this leads to to a reduction in mechanical strength (embrittlement, low Bending elasticity) of the material.

PCT / EP92 / 00959 tries to avoid these difficulties, by reacting starch with copolymers on the one hand and Structure is tried by adding monomeric dispersants too homogenize. However, this approach leads to a high one synthetic effort, since copolymers have to be prepared first and During the extrusion, monomeric auxiliaries are added in a precisely defined amount Need to become. This makes these materials very expensive and theirs Marketing difficult.

JP 52121096 describes the formation of inclusion compounds Cyclodextrin rings with α-ω-diamines and their subsequent esterification with α-ω-dicarboxylic acid chlorides to polyamides of the A-B type described. Cyclodextrins are cyclic oligomers of amylose and consist of 6, 7 or 8 glucose units (α, β, γ cyclodextrin) [G. Wenz, Angew. Chem. 1994, 106, 851-870; Appl. Chem. Int. Ed. Engl., 33, 803-822]. The polymerization will thereby as an interface reaction at a water-chloroform interface carried out. According to this process, the polymer chain can contain up to 50% be covered with cyclodextrin rings. Problems with possible use this process prepares the relatively high price of acid chlorides, on the other hand, the use of large amounts of halogenated solvents is over economic and environmental aspects justifiable because of the biological properties that are environmentally friendly degradable polymers from renewable raw materials be made.  

Further studies on polymeric inclusion compounds have been made by Harada, Gibson and Wenz. The first systematic studies on polymeric inclusion compounds dealt with the interaction of cyclodextrins and water-soluble polymers. For example, Harada et al. the threading of α-cyclodextrin on poly (ethylene glycol) and poly (trimethylene oxide) of β-cyclodextrin on polypropylene oxide and of γ-cyclodextrin on poly (methyl vinyl ether) have been demonstrated [A. Harada, J. Li, M. Kamachi, Macromolecules 1993, 26, 5698-5703]. Almost water-insoluble polymers such as poly (isobutene) could also be enclosed in cyclodextrins by ultrasonication [A. Harada, J. Li, S. Suzuki, M. Kamachi, Macromolecules 1993, 26, 5267-5268]. Obviously, polymeric inclusion compounds are only formed if the thickness of the polymer fits exactly inside the cyclodextrin. In addition, the formation of these inclusion compounds does not occur with short (P _n <10) and very long polymer chains (P _n <100). All of these polymer inclusion compounds are insoluble in water and most organic solvents. They dissolve only in dissociation in strongly polar solvents like DMSO. The first soluble polymeric cyclodextrin inclusion compounds were obtained from Wenz and Keller from poly (iminooligomethylenes) or ions [G. Wenz, B. Keller, Angew. Chem. 1992, 104, 201-204; Appl. Chem. Int. Ed. EngL, 31, 197-199]. This was the first time to quantitatively investigate the kinetics of threading the cyclodextrin rings onto polyamine chains. Depending on the concentration, the degree of occupancy of the chain was 0.2-0.8 rings per repetition unit. However, this process for the production of soluble polymeric inclusion compounds remained limited to relatively few polymers, since several structural requirements must be met by the polymer (high water solubility, hydrophobic binding sites, small thickness). However, all these processes have in common that they start from a polymer which is coated with cyclodextrin rings.

The polymerization of monomers in host crystals (clathrates) was indeed has already been described several times, but always low molecular weight was not annular molecules such as urea, thiourea, deoxycholic acid [M. Miyata, Y. Kitahara, K. Takemoto, Polymer J. 1981, 13, 111-113] or Perhydrotriphenyls [M. Farina, U. Pedretti, M. T. Gramegna, G. Audisio, Macromolecules 1970, 3, 475-480] used as matrices. In these were Monomers such as butadiene and its derivatives are radically polymerized. At the Dissolving the polymers disintegrates the supramolecular structure.

The object of the present invention is a polymeric material To provide, which avoids the disadvantages mentioned, that is, on raw materials based on natural resources, preferably arable plants, can be obtained, the production of which is as simple as possible without Solvent is difficult to dispose of and is a high one Possesses strength.

This object is achieved in that a method is provided for Preparation of polymeric inclusion compounds from cyclic or cyclizable host molecules and polymerizable guest molecules. The Host molecules can be made from native or chemically converted amylose or Cyclodextrins, which are guest molecules made from polymers of monomers that convert the host molecules into a crystalline channel structure and within polymerize this channel structure.

Here host molecules are understood to be molecules, the three-dimensional ones Structures, for example helical structures, can form their cavities can be taken by the guest molecules. The following will be these three-dimensional structures are called channel structures. Host molecules can be, for example, α-, β- or γ-cyclodextrins or starch be. More generally speaking, the host molecules consist of native or chemically modified amylose. Polymerizable guest molecules can  be, for example, polyamides, in particular linear, branched or cyclic ω-aminocarboxylic acids with 6 to 22 carbon atoms, too May contain double bonds. Furthermore come as guest molecules linear, branched or cyclic α, ω-dicarboxylic acids and / or α, ω-diamines with 6 to 22 carbon atoms in question.

Under a polymeric inclusion compound here becomes a copolymer understood from a polymer that forms a channel structure (host molecule) and a polymer located in the cavities of the channel structure (Guest molecule).

The method enables the guest molecule to bond to the Host molecule succeeds without domain formation and at the same time a preceding one Copolymer synthesis is avoided.

It is essential to the invention that the guest molecules in monomeric form with the Host molecule are brought together. Polymerization of the guest molecules only takes place if this is already within the channel structures of the Host molecules. For example, α, ω-aminocarboxylic acids in the Channel structure to be polymerized to include polyamides. It was Surprisingly, the cyclodextrin rings have sufficient thermal stability for the polycondensation, and that the polycondensation while maintaining the channel structure.

The new process for the production of polymeric inclusion compounds is characterized by great simplicity, high occupancy of the polymer chain and good solubility of the products. The degree of occupancy is understood to mean the numerical ratio of the monomer building blocks of the host molecule to the monomer building blocks of the guest molecule. The degree of coverage of the polymeric inclusion compounds according to the invention is preferably between 1 and 4. The polymer chain is synthesized by polycondensation of included monomer units in the crystal structure of the host molecule (see FIG. 1). Polyamides, and especially polyamide-11, which are derived from the oil of the castor bean plant [M.Genas, Angew. Chem., 74, (1962), 535]. Polyamides such as nylon-6 (poly- (caprolactam)), nylon-6,6 (poly- (hexamethylene-adipic acid diamide)) or nylon-11 (poly- (undecanoic acid amide)) have great practical importance because of their high dimensional stability and their high melting point acquired. However, due to strong intermolecular hydrogen bonds, these polymers are insoluble in most solvents apart from concentrated sulfuric acid and trifluoroacetic acid, which makes their processing very difficult. Polyamides are produced industrially either by ring-opening polymerization of the corresponding lactam or by polycondensation of the salt from amine and acid components (AH salt) at high temperature in bulk. According to the invention, water-soluble polymeric inclusion compounds can be prepared by polycondensation of insoluble AH salts in the presence of cyclodextrins or starch.

The process for the preparation of inclusion compounds according to the invention generally works as follows. The host molecule will dissolved in water together with the monomeric guest molecule and at 70 ° C to 100 ° C, preferably to 80 ° C to 95 ° C, heated. Then quickly cooled, that is, to a temperature within about 10 to 30 minutes from about 0 ° C to 20 ° C, preferably 2 ° C to 8 ° C. The product can also by Precipitation can be obtained. The precipitate is filtered off and dried. Man receives a light powder. This is in a vacuum (<1000 Pa, preferably <100 Pa) for 1 to 10 hours, preferably 3 to 5 h at a temperature of 150 ° C to 250 ° C, preferably 200 ° C to 240 ° C, exposed, the guest molecules polymerize.  

To produce inclusion compounds according to the invention, α, ω-aminocarboxylic acids, in particular aminoundecanoic acid, hereinafter abbreviated to 2 a, are preferably used as the guest molecule. These are heated with the native or chemically modified amylose, which serves as the host molecule, for example with α-cyclodextrin ( 1 a) in aqueous solution and cooled rapidly.

For guest molecules with more than 6 methylene groups, the inclusion compound crystallizes out in 65% yield. It is technically important that the mother liquor can be circulated, so that 100% process yield is achieved. Depending on the molar ratio of cyclodextrin and amino acid, a guest molecule is built into one or two cyclodextrin molecules. 4- (Aminomethyl) benzoic acid (5) also forms an inclusion compound with cyclodextrin (see FIG. 2). Similarly, crystalline ternary inclusion compounds with defined stoichiometry are obtained from α, ω-diamines and α, ω-dicarboxylic acids and α-cyclodextrin (see FIG. 2). The same molar amounts of acid and amine are incorporated, as is the case with the crystallization of AH salts without cyclodextrin. These ternary inclusion compounds are also capable of polycondensation to include enclosed polyamides.

In a particularly preferred embodiment, starch, in particular soluble starch, used as a host molecule. Because starch is a natural product a broad molecular weight distribution, no exact assignment of the Monomers can be specified.

In the case of polymeric inclusion compounds according to the invention made from cyclodextrin and polyamide makes the polyamide about 5-10 mol%, in the case of polymers Inclusion connections made of starch and polyamide make the polyamide between 30 and 70 mol% of the inclusion compound.  

So solid polycondensation between amino and acid groups can take place, these functional groups must be adjacent to each other. This is possible in a channel-like packing of the cyclodextrin rings. X-ray diffractograms of the inclusion compounds actually lay one channel-like packing close. The reflections at 19.63 ° (d = 4.53 Å) agree those of the inclusion compound of dodecaethylene glycol and α-cyclodextrin match [A. Harada, J. Li, M. Kamachi, Macromolecules 1994, 27, 4538-4543]. For the latter, a channel-like structure was determined by an X-ray structure analysis proven.

The occurrence of discrete reflections at 5.360 (d = 16.47 Å), 22.330 (d = 3.98 Å) and 23.390 (d = 3.81 Å) also suggests that it was in the case of the inclusion compound with strength is a defined, tubular structure. To carry out the polycondensation, the microcrystalline inclusion compounds are annealed at 150-250 ° C. in vacuo. The polymerization can easily be monitored in the IR spectrum by means of the formation of the amide band at 1732 cm ^-1 . Irrespective of this, the yield of polyamide was determined gravimetrically after the cyclodextrin had been boiled in 1% hydrochloric acid. By using bulky undecanoic acid amides such as 11-piperizylundecanoic acid or 11- (2-methyl) -piperizylundecanoic acid, the threading off of the rings can be slowed down and the dissolution time increased. Obviously the condensation starts abruptly at 200 ° C. A further increase in temperature leads to a strong acceleration of the reaction. Above 250 ° C, in addition to the condensation, massive cyclodextrin or starch decomposition occurs. In almost all inclusion compounds, the polycondensation takes place to almost complete. The polymerization can also be carried out in the extruder. If the polymeric inclusion compounds according to the invention are to be coextruded with other polymers, the outlay can be considerably reduced.

The high sales achieved indicate an alternating sequence of amino and Acid groups, since an orientation reversal in the crystal channel is certain can be excluded. The alternation must be strong Interactions between amino and acid groups during the Crystallization can be attributed. X-ray diffractograms also show that the crystalline order is retained in the case of cyclodextrin.

It was completely surprising that the resulting polyamide-α-cyclodextrin inclusion compounds can be water-soluble. The solubility in water can be controlled, for example via the weight ratio. The ¹H-NMR spectrum of 2a · (1a) ₂ ( Fig. 4) shows the signals of cyclodextrin and polyamide. The good solubility of the polymeric inclusion compound is due to the high occupancy of the polymer chain with cyclodextrin. In the case of nylon-11, an occupancy level of 2 can be achieved, i.e. two units of cyclodextrin per repetition unit. When reacting diaminoeicosan as a guest molecule with eicosanedicarboxylic acid as a host molecule, a degree of occupancy of 4 can be achieved.

After a few hours, most systems produce a precipitate in which the polyamide is enriched. Obviously, the solubilizing cyclodextrins slowly thread off, causing free polymer chain ends to aggregate and lead to insolubility. Rings that are still threaded can no longer thread due to the lack of mobility. The polymer with the dimethylpiperazine building blocks ( 4 ) is even soluble in water to an unlimited extent. Consequently, the methyl substituents on the piperazine prevent the rings from sliding off the polymer chain. Through mixed crystal formation from slim and bulky building blocks z. B. (2a, 4 · (1a) ₂) can be generated in principle polymers with blocking groups in which the solubility period is adjustable.

The starch and nylon inclusion joints are for technical Applications of greatest interest since according to the invention  Procedure of interlocking nylon and starch without any additives succeed. Stable polymer blends, ie Produce mixed polymers from at least two different building blocks, which do not have the disadvantages caused by segregation. It can the synthesis of copolymers can be dispensed with. The required Environmentally friendly production of the polymer blends is also given, since only Water is used as a solvent. In principle, the process is not only applicable to the polyamides described here and their monomers. Much more are all polymerizable guest compounds in which the Polymerization reaction can be carried out so that undesirable Side reactions such as the attack on the host lattice by the polymerizing Guest can be avoided. So are conjugate linear, or with short ones Side chain substituted monomer conceivable in the crystal channel of Cyclodextrins can be radically polymerized, for example. Besides are dialdehydes or diketones in question, which are combined with diamines poly (Schiff Bases) can form.

In addition to starch and cyclodextrins, all cyclic or Cyclizable compounds in question, which are capable of polymerizable To complex guest connections and in the form of channel structures crystallize. Cellulose can also be used as a host molecule.

The mechanical properties of those produced according to the invention Mixed polymers can be varied, for example by adjusting the Degree of occupancy, i.e. the quantitative relationship between host and Guest molecule. Furthermore, the inclusion compounds can further polymers are admixed, such as separate host and / or guest molecule or other polymers.

Because of the good mechanical properties that can be varied over a wide range Properties of the inclusion compounds and those containing them  Mixed polymers, these are applicable in many areas. For example can films, packaging or insulating materials be made from it, or also disposable items such as dinnerware or cutlery. The material can be also coextrude with other polymers.

Another application, especially the cyclodextrin polyamide Inclusion compounds is the surface coating of nylon materials for hydrophilizing the material. The polymer chains are also stored their free segments on the polymer and occupied the cyclodextrin Loops hydrophilize the surface. Conversely, you can Starch cellulose materials, such as cotton or linen, through the Polyamide content are hydrophobized. It is also a coating of Garments possible to z. B. To make linen non-iron.

The invention is explained in more detail with reference to FIGS. 1 to 4. Fig. 1 shows an example of the structure of inclusion compounds from cyclodextrin as the host molecule and polyamide as the guest molecule.

In FIG. 2, data are listed of various inventively produced inclusion compounds with the host molecule α-cyclodextrin (1 a). The abbreviations are defined in the description. The weight ratio is the molar ratio of host molecule to guest molecule.

Fig. 3 shows the NMR spectrum of the monomeric inclusion complex of 11-aminoundecanoic acid and α-cyclodextrin.

Fig. 4 shows the NMR spectrum of the polymeric inclusion complex of 11-aminoundecanoic acid and α-cyclodextrin.

In the following, the invention will be explained in more detail on the basis of exemplary embodiments explained.

example 1 Representation of the cyclodextrin inclusion compound using the example 2a · (1a) ₂

5 g of aminoundecanoic acid ( 2 a) and 125 g of α-cyclodextrin ( 1 a) are dissolved in 250 ml of water and heated to 80 ° C. with stirring. After a short time, the solution becomes clear, whereupon it is cooled to 5 ° C. The white precipitate that forms is filtered off and washed with 400 ml of water. After drying in vacuo 39.8g, (65%) 2a · (1a) ₂ are obtained.

Structure detection: 1 H-NMR (DMSO / AcOD): 4.33 (d, 12 H, J = 1.73 Hz, H-1), 3.29 (t, 12H, J = 8.9 Hz, H-3), 3.18 (m, 36 H, H-5.6), 2.92 (t, 12H, J = 8.86 Hz, H-4), 2.816 (dd, 12H, J _1-2 = 1.73 Hz, J _2-3 = 8.86 Hz, H-2), 2.28 (t, 1.7H, J = 7.38 Hz, Ha), 2.04 (AcOD) 1.70 (t, 1.7H, J = 7.39 Hz, Hj), 1.02 (m, 3.7H, Hb, i), 0.775 (s, 12H, H-ch) ppm.
IR: 3408s, 2925s, 1635m, 1410w, 1362w, 1291w, 1246w, 1202w, 1162s, 1095s, 938m cm ^-1 .
EA: calc.: C 46.43%, H 6.71%, N 0.65%, found: C 45.52%, H 7.03%, N 1.03%.

Example 2 Preparation of the cyclodextrin inclusion compound Sebacic acid, diaminodecane and α-cyclodextrin

5g diaminodecane, 0.58g sebacic acid and 16.4g α-cyclodextrin are in 50 ml of water dissolved and heated to 80 ° C with stirring. After a short time the Solution clear, then put it in the fridge. The overnight the white precipitate which forms is filtered off and washed with 150 ml of water. After drying in vacuo, 4.72g, (38.3%) of Inclusion connection received.  

Structure detection: 1 H-NMR (DMSO / AcOD): 4.33 (d, 12 H, J = 1.73 Hz, H-1), 3.29 (t, 15H, J = 8.86 Hz, H-3), 3.16 (m, 45 H, H-5.6), 2.91 (t, 15H, J = 8.86 Hz, H-4), 2.81 (dd, 12H, J _1-2 = 1 , 73 Hz, J _2-3 = 8.86 Hz, H-2), 2.28 (t, 1.85 H, J = 7.38 Hz, Ha), 2.04 (AcOD) 1.70 (t, 1.7H , J = 7.39 Hz, Ha ′), 1.00 (m, 4.4 H, Hb, i), 0.775 (s, 12 H, Hch) ppm.
IR: 3383s, 2923s, 1644w, 1550w, 1404w, 1361w, 1291w, 1205w, 1148s, 1038s, 938m, 756w, 610w, 570w cm ^-1 .

Example 3 Representation of the starch inclusion compound using the example of 2a starch

0.3 g of aminoundecanoic acid ( 2 ) and 3 g of α-cyclodextrin ( 1 a) are dissolved in 40 ml of water and heated to 80 ° C. with stirring. After a short time, the solution becomes opal, after which it is cooled to 5 ° C. The white precipitate which forms overnight is filtered off and washed with 100 ml of water. After drying in vacuo, 1.42 g, 2a starch are obtained.

Structure detection: 1 H-NMR (DMSO / AcOD): 4.59 (s, 2.6 H, H-1), 3.20-2.90 (b, 10 H, H-3, 5, 6), 2 , 90-2.70 (b, 5H, H-2, 4), 2.24 (b, 2H, Ha), 1.67 (b, 2H, Hj), 0.98 (b, 4H, Hb , i), 0.74 (b, 12H, Hch) ppm.
IR: 3404s, 2930s, 1644m, 1556m, 1162s, 1087s, 1064s, 949m, 860m, 704w, 574w cm ^-1 .

Example 4 Representation of the polymeric inclusion compound using the example p- (2a · (1a) ₂)

203mg 2a · (1a) ₂ are placed in a test tube and in one at 210 ° C preheated oven under oil pump vacuum implemented for five hours. You get 196mg (97.4%) p- (2a · (1a) ₂).  

Structure detection: 1 H NMR (D2O): 5.08 (s, 12 H, H-1), 4.0-3.75 (b, 52 H, H-3, 5, 6), 3.75-3 , 50 (b, 25.4H, H-2, 4), 3.0 (b, 2H, Ha), 2.30-2.05 (b, 2H, Hj), 1.75-1.6 (b, 4H, Hb, i), 1.50-1.15 (b, 12H, Hch) ppm.
IR: 3399s, 2925s, 2362w, 1733m, 1646m, 1410w, 1362w, 1161s, 1087s, 938m, 862w, 755w, 706w, 703w, 579m cm ^-1 .
EA: calc.: C 46.83%, H 6.68%, N 0.66%, found: C 45.61%, H 6.76%, N 1.13%,

Example 5 Degradation of the polymeric inclusion compound using the example of p- (2. (1a) ₂)

1.172g p- (2a · (1a) ₂) are dissolved in 60ml 1% hydrochloric acid and over 25 Hours at 80 ° C implemented. The product obtained is filtered off and washed several times with water and methanol. You get 103.1mg (93.9%) Nylon-11.

Structure detection: 1 H-NMR (D2O): 2.87 (b, 22 H, Ha), 1.96 (b, 2 H, Hj), 1.71-1.66 (impurity), 1.19-1, 10 (b, 4H, Hb, i), 0.82 (b, 12H, Hch) ppm.
IR: 3399s, 2935s, 2853m, 2359w, 1734m, 1644m, 1556m, 1157m cm ^-1 .

Claims (17)

1. polymeric inclusion compounds from host molecules and guest molecules, taking the host molecules from native or chemically converted amylose and the guest molecules consist of polymers of monomers which are the Convert host molecules into a channel structure and within it Polymerize channel structure. 2. Polymeric inclusion compounds according to claim 1, characterized, that the host molecules are α, β- or γ-cyclodextrin. 3. polymeric inclusion compounds according to claim 1, characterized, that the host molecule is starch. 4. Polymeric inclusion compounds according to any one of claims 1 to 3 characterized, that the guest molecules are polyamides. 5. Polymeric inclusion compounds according to any one of claims 1 to 3 characterized, that the monomers of the guest molecules are linear, branched or cyclic ω- Are amino carboxylic acids having 6 to 22 carbon atoms. 6. Polymeric inclusion compounds according to any one of claims 1 to 3 characterized, that the monomers of the guest molecules are linear, branched or cyclic α, ω- Dicarboxylic acids and / or α, ω-diamines each having 6 to 22 carbon atoms.   7. Mixed polymers containing the polymeric inclusion compounds according to one of claims 1 to 6. 8. Process for the preparation of polymeric inclusion compounds according to one of claims 1 to 6, characterized, that host molecules and guest molecules are heated in a solvent and then cooled or precipitated, then filtered and dried and then the guest molecules at pressures below 1000 Pa at one Temperature of 150 ° C to 250 ° C are polymerized. 9. The method according to claim 8, characterized, that the solvent is water. 10. The method according to one or more of claims 8 to 9, characterized, that host molecules and guest molecules in a solvent at temperatures be heated between 50 ° C and 130 ° C. 11. The method according to one or more of claims 8 to 10, characterized, that host molecules and guest molecules in a solvent at temperatures be heated between 70 ° C and 95 ° C. 12. The method according to one or more of claims 8 to 11, characterized, that the host molecules and guest molecules after heating to a Temperature between 0 ° C and 20 ° C to be cooled.   13. The method according to one or more of claims 8 to 12, characterized, that the host molecules and guest molecules after heating to a Temperature between 2 ° C and 8 ° C to be cooled. 14. The method according to one or more of claims 8 to 13, characterized, that the polymerization is carried out at pressures below 100 Pa. 15. The method according to one or more of claims 8 to 14, characterized, that the polymerization of the guest molecules at temperatures between 200 ° C. and 240 ° C is carried out. 16. The method according to one or more of claims 8 to 15, characterized, that the cooling process is completed in less than 30 minutes. 17. The method according to claim 8, characterized, that the polymerization takes place during extrusion.